1、Designation: D5185 09D5185 13 An American National StandardStandard Test Method forMultielement Determination of Additive Elements, WearMetals, and Contaminants in Used Used and UnusedLubricating Oils and Determination of Selected Elements inBase Oils by Inductively Coupled Plasma Atomic EmissionSpe
2、ctrometry (ICP-AES)1This standard is issued under the fixed designation D5185; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript e
3、psilon () indicates an editorial change since the last revision or reapproval.This standard has been approved for use by agencies of the Department of Defense.INTRODUCTIONCosts associated with maintenance due to engine and machine wear can be significant. Therefore,diagnostic methods for determining
4、 the condition of engines and other machinery can be important.This test method is intended to quantify, for the purpose of equipment monitoring, the concentrationof metals in used lubricating oils. Although the precision statement was determined by analyzing avariety of used oils this test method c
5、an, in principle, be used for the analysis of unused oils to providemore complete elemental composition data than Test Methods D4628, D4927, or D4951.1. Scope*1.1 This test method covers the determination of additive elements, wear metals, and contaminants in used and unusedlubricating oils and base
6、 oils by inductively coupled plasma atomic emission spectrometry (ICP-AES). The specific elements arelisted in Table 1.1.2 This test method covers the determination of selected elements, listed in Table 1, in re-refined and virgin base oils.1.3 For analysis of any element using wavelengths below 190
7、 nm, a vacuum or inert-gas optical path is required. Thedetermination of sodium and potassium is not possible on some instruments having a limited spectral range.1.4 This test method uses oil-soluble metals for calibration and does not purport to quantitatively determine insolubleparticulates.Analyt
8、ical results are particle size dependent, and low results are obtained for particles larger than a few micrometers.21.5 Elements present at concentrations above the upper limit of the calibration curves can be determined with additional,appropriate dilutions and with no degradation of precision.1.6
9、For elements other than calcium, sulfur, and zinc, the low limits listed in Table 2 and Table 3 were estimated to be ten timesthe repeatability standard deviation. For calcium, sulfur, and zinc, the low limits represent the lowest concentrations tested in theinterlaboratory study.1.7 The values stat
10、ed in SI units are to be regarded as standard. No other units of measurement are included in this standard.1.8 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibilityof the user of this standard to establish appropriate safety a
11、nd health practices and determine the applicability of regulatorylimitations prior to use. Specific warning statements are given in 6.1, 8.2, and 8.4.1 This test method is under the jurisdiction of ASTM Committee D02 on Petroleum Products Products, Liquid Fuels, and Lubricants and is the direct resp
12、onsibility ofSubcommittee D02.03 on Elemental Analysis.Current edition approved April 15, 2009Sept. 15, 2013. Published May 2009September 2013. Originally approved in 1991. Last previous edition approved in 20052009as D5185D5185 09.05. DOI: 10.1520/D5185-09.10.1520/D5185-13.2 Eisentraut, K. J., Newm
13、an, R. W., Saba, C. S., Kauffman, R. E., and Rhine, W. E., Analytical Chemistry, Vol 56, 1984.This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Becauseit may not be technically poss
14、ible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current versionof the standard as published by ASTM is to be considered the official document.*A Summary of Changes section appears at the end of this standardCop
15、yright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States12. Referenced Documents2.1 ASTM Standards:3C1109 Practice for Analysis of Aqueous Leachates from Nuclear Waste Materials Using Inductively Coupled Plasma-AtomicEmission SpectroscopyD1552 Te
16、st Method for Sulfur in Petroleum Products (High-Temperature Method)D4057 Practice for Manual Sampling of Petroleum and Petroleum ProductsD4307 Practice for Preparation of Liquid Blends for Use as Analytical StandardsD4628 Test Method for Analysis of Barium, Calcium, Magnesium, and Zinc in Unused Lu
17、bricating Oils by Atomic AbsorptionSpectrometryD4927 Test Methods for Elemental Analysis of Lubricant and Additive ComponentsBarium, Calcium, Phosphorus, Sulfur,and Zinc by Wavelength-Dispersive X-Ray Fluorescence Spectroscopy3 For referencedASTM standards, visit theASTM website, www.astm.org, or co
18、ntactASTM Customer Service at serviceastm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Document Summary page on the ASTM website.TABLE 1 Elements Determined and Suggested WavelengthsAElement Wavelength, nmAluminum 308.22, 396.15, 309.27Barium 233.53, 455.40, 493.4
19、1Boron 249.77Calcium 315.89, 317.93, 364.44, 422.67Chromium 205.55, 267.72Copper 324.75Iron 259.94, 238.20Lead 220.35Magnesium 279.08, 279.55, 285.21Manganese 257.61, 293.31, 293.93Molybdenum 202.03, 281.62Nickel 231.60, 227.02, 221.65Phosphorus 177.51, 178.29, 213.62, 214.91, 253.40Potassium 766.49
20、Sodium 589.59Silicon 288.16, 251.61Silver 328.07Sulfur 180.73, 182.04, 182.62Tin 189.99, 242.95Titanium 337.28, 350.50, 334.94Vanadium 292.40, 309.31, 310.23, 311.07Zinc 202.55, 206.20, 213.86, 334.58, 481.05A These wavelengths are only suggested and do not represent all possiblechoices.TABLE 2 Repe
21、atabilityElement Range, mg/kg Repeatability, g/gAAluminum 640 0.71 X0.41Barium 0.54 0.24 X0.66Boron 430 0.26 XCalcium 409000 0.0020 X1.4Chromium 140 0.17 X0.75Copper 2160 0.12 X0.91Iron 2140 0.13 X0.80Lead 10160 1.6 X0.32Magnesium 51700 0.16 X0.86Manganese 5700 0.010 X1.3Molybdenum 5200 0.29 X0.70Ni
22、ckel 540 0.52 X0.49Phosphorus 101000 1.3 X0.58Potassium 401200 3.8 X0.33Silicon 850 1.3 X0.26Silver 0.550 0.15 X0.83Sodium 770 0.49 X0.66Sulfur 9006000 0.49 X0.81Tin 1040 2.4 X0.17Titanium 540 0.54 X0.37Vanadium 150 0.061 XZinc 601600 0.15 X0.88A where: X = mean concentration, g/g.D5185 132D4951 Tes
23、t Method for Determination of Additive Elements in Lubricating Oils by Inductively Coupled Plasma AtomicEmission SpectrometryD7260 Practice for Optimization, Calibration, and Validation of Inductively Coupled Plasma-Atomic Emission Spectrometry(ICP-AES) for Elemental Analysis of Petroleum Products a
24、nd LubricantsE135 Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials3. Terminology3.1 Definitions:3.1.1 emission spectroscopyrefer to Terminology E135.3.2 Definitions of Terms Specific to This Standard:3.2.1 additive elementa constituent of a chemical compound that
25、improves the performance of a lubricating oil.3.2.2 analytean element whose concentration is being determined.3.2.3 Babington-type nebulizera device that generates an aerosol by flowing a liquid over a surface that contains an orificefrom which gas flows at a high velocity.3.2.4 calibrationthe proce
26、ss by which the relationship between signal intensity and elemental concentration is determined fora specific element analysis.3.2.5 calibration curvethe plot of signal intensity versus elemental concentration using data obtained by makingmeasurements with standards.3.2.6 contaminanta foreign substa
27、nce, generally undesirable, introduced into a lubricating oil.3.2.7 detection limitthe concentration of an analyte that results in a signal intensity that is some multiple (typically two) timesthe standard deviation of the background intensity at the measurement wavelength.3.2.8 inductively-coupled
28、plasma (ICP)a high-temperature discharge generated by flowing an ionizable gas through amagnetic field induced by a load coil that surrounds the tubes carrying the gas.3.2.9 linear response rangethe elemental concentration range over which the calibration curve is a straight line, within theprecisio
29、n of the test method.3.2.10 profilinga technique that determines the wavelength for which the signal intensity measured for a particular analyte isa maximum.3.2.11 radio frequency (RF)the range of frequencies between the audio and infrared ranges (3 kHz to 300 GHz).3.2.12 wear metalan element introd
30、uced into the oil by wear of oil-wetted parts.4. Summary of Test Method4.1 A weighed portion of a thoroughly homogenized used oil or unused lubricating oil, or base oil, is diluted tenfold by weightwith mixed xylenes or other suitable solvent. Standards are prepared in the same manner.An optionalAma
31、ndatory internal standardTABLE 3 ReproducibilityElement Range, mg/kg Reproducibility, g/gAAluminum 640 3.8 X0.26Barium 0.54 0.59 X0.92Boron 430 13 X0.01Calcium 409000 0.015 X1.3Chromium 140 0.81 X0.61Copper 2160 0.24 XIron 2140 0.52 X0.80Lead 10160 3.0 X0.36Magnesium 51700 0.72 X0.77Manganese 5700 0
32、.13 X1.2Molybdenum 5200 0.64 X0.71Nickel 540 1.5 X0.50Phosphorus 101000 4.3 X0.50Potassium 401200 6.6 X0.29Silicon 850 2.9 X0.39Silver 0.550 0.35 XSodium 770 1.1 X0.71Sulfur 9006000 1.2 X0.75Tin 1040 2.1 X0.62Titanium 540 2.5 X0.47Vanadium 150 0.28 X1.1Zinc 601600 0.083 X1.1A where: X = mean concent
33、ration, g/g.D5185 133can be is added to the solutions to compensate for variations in test specimen introduction efficiency. The solutions are introducedto the ICP instrument by free aspiration or an optional peristaltic pump. By comparing emission intensities of elements in the testspecimen with em
34、ission intensities measured with the standards, the concentrations of elements in the test specimen are calculable.4.2 Standard operating parameters and other considerations to be considered in using ICP-AES technique are given in PracticeD72605. Significance and Use5.1 This test method covers the r
35、apid determination of 22 elements in used and unused lubricating oils and in base oils, and itprovides rapid screening of used oils for indications of wear. Test times approximate a few minutes per test specimen, anddetectability for most elements is in the low mg/kg range. In addition, this test me
36、thod covers a wide variety of metals in virginand re-refined base oils. Twenty-two elements can be determined rapidly, with test times approximating several minutes per testspecimen.5.2 When the predominant source of additive elements in used lubricating oils is the additive package, significant dif
37、ferencesbetween the concentrations of the additive elements and their respective specifications can indicate that the incorrect oil is beingused.The concentrations of wear metals can be indicative of abnormal wear if there are baseline concentration data for comparison.A marked increase in boron, so
38、dium, or potassium levels can be indicative of contamination as a result of coolant leakage in theequipment. This test method can be used to monitor equipment condition and define when corrective actions are needed.5.2.1 The significance of metal analysis in used lubricating oils is tabulated in Tab
39、le 4.5.3 The concentrations of metals in re-refined base oils can be indicative of the efficiency of the re-refining process. This testmethod can be used to determine if the base oil meets specifications with respect to metal content.6. Interferences6.1 SpectralCheck all spectral interferences expec
40、ted from the elements listed in Table 1. Follow the manufacturers operatingguide to develop and apply correction factors to compensate for the interferences. To apply interference corrections, allconcentrations must be within the previously established linear response range of each element listed in
41、 Table 1.(. (WarningCorrect profiling is important to reveal spectral interferences from high concentrations of additive elements on the spectral linesused for determining wear metals.)6.1.1 Spectral interferences can usually be avoided by judicious choice of analytical wavelengths. When spectral in
42、terferencescannot be avoided, the necessary corrections should be made using the computer software supplied by the instrument manufactureror the empirical method described below. Details of the empirical method are given in Test Method C1109 and by Boumans.4 Thisempirical correction method cannot be
43、 used with scanning spectrometer systems when both the analytical and interfering linescannot be located precisely and reproducibly. With any instrument, the analyst must always be alert to the possible presence ofunexpected elements producing interfering spectral lines.4 Boumans, P. W. J. M., “Corr
44、ections for Spectral Interferences in Optical Emission Spectrometry with Special Reference to the RF Inductively Coupled Plasma,”Spectrochimica Acta, 1976, Vol 31B, pp. 147152.TABLE 4 Wear Metals (Elements) in Used Lubricating OilsElements Wear IndicationArgon Wrist pin bearings in railroad and auto
45、 engines, silver plotted spline lubricating pumpAluminum Piston and bearings wear, push rods, air cooler, pump hosings, oil pumps, gear castings, box castingsBoron Coolant leakage in systemCadmium BearingsChromium Ring wear, cooling system leakage, chromium-plated parts in aircraft engines, cylinder
46、 liners, seal ringsCopper Wear in bushings, injector shields, coolant core tubes, thrust washers, valve guides, connecting rods, piston rings, bearings, sleeves,bearing cagesIron Wear from engine block, cylinder, gears, cylinder liners, valve guides, wrist pins, rings, camshaft, oil pump, crankshaft
47、, ball and rollerbearings, rustMagnesium Cylinder liner, gear box housings in aircraft enginesMolybdenum Wear in bearing alloys and in oil coolers; various molybdenum-alloyed components in aircraft engines, piston ringsSodium Antifreeze leakageNickel Bearings, valves, gear platingsLead Bearings, fue
48、l blowby, thrust bearings, bearing cages, bearing retainersAntimony Crankshaft and camshaft bearingsSilicon Dirt intrusion from improper air cleaner, seal materialsTin Bearings and coatings of connecting rods and iron pistonsTitanium Various titanium-alloyed components in aircraft enginesTungsten Be
49、aringsZinc Neoprene seals, galvanized pipingD5185 1346.1.2 The empirical method of spectral interference correction uses interference correction factors. These factors are determinedby analyzing the single-element, high-purity solutions under conditions matching as closely as possible those used for testspecimen analysis. Unless plasma conditions can be accurately reproduced from day to day, or for longer periods, interferencecorrection factors found to affect the results significantly must be redetermined eac
